Patent GB-880923-A (GB)
Title: Improvements in and relating to polymers
IPC: C08G65/26
Filed: 1958-04-17
Abstract: A mixture of oxyalkylene-carboxyalkylene polymers having chains of oxyalkylene links interrupted by monocarboxyalkylene links, the oxyalkylene links in said chains each including a terminal oxy group, a terminal carbon atom and one intermediate carbon atom, and the monocarboxyalkylene links in said chains each including a terminal carboxy group, a terminal carbon atom and a chainlet of at least two intermediate carbon atoms, the terminal oxy and carboxy groups of said links being connected to the terminal carbon atoms of next adjacent links, said mixture having an average molecular weight of at least 400, is made by reacting a lactone having at least four carbon atoms in the ring, or a hydroxy ester thereof, with a 1, 2-epoxide and a polyfunctional compound having at least two reactive hydrogens that are capable of opening a lactone ring or a 1, 2-epoxide ring at a temperature of 10 DEG  C. to 200 DEG  C.  Specified lactones are S -caprolactone, alkyl substituted S -caprolactone, delta valerolactone, g -butyrolactone, alkoxy S -caprolactones, aryl and aralkyl S -caprolactone, zetaenantholactone and eta-caprylolactone. Specified 1, 2-epoxides are ethylene oxide, propylene oxide, 1-methyl-1, 2-propylene oxide, 1, 2-butylene oxide, butadiene monoxide, epichlorohydrin, glycidol, cyclohexene oxide and styrene oxide and diepoxides, e.g. butadiene dioxide, vinyl cyclohexene dioxide, dicyclopentadiene oxide, 3, 4-epoxy-6-methylcyclohexyl -3, 4-epoxy-6-methyl-cyclohexane-carboxylate and glycidyl ethers of polyhydric phenols.  Specified polyfunctional compounds are polyfunctional alcohols, amines, mercaptans, phenols, amino alcohols and mercapto alcohols, e.g. 2, 2-dimethyl-1, 3-propane diol, 3-methyl-1, 5-pentane diol, cyclohexane diols, hydroquinone, xylene diols, 1, 4-piperazine diethanol, ethanolamine, p-amino-a -methyl benzyl alcohol, 4-aminocyclohexanol, p-phenylene diamine, benzidine, 2, 7-fluorene diamine, piperazine, glycerol, pentaerythritol, glucose, sucrose, cellulose, diethylene triamine, adipic acid, 6-aminocaproic acid and citric acid, many other compounds being specified.  The products of the invention may be reacted with an excess of a dibasic acid or anhydride. Polyurethane elastomers and foams may be made by reacting the hydroxy terminated polymers of the invention with isocyanates. Specified promotion catalysts for the process of the invention are the halides of boron, aluminium, tin, cadmium, antimony, beryllium, bismuth, cadmium, gallium, iron, uranium, zinc and zirconium.  In one method of effecting the process of the invention, a reaction product from the lactone and a molar excess of a monohydric alcohol is reacted with an epoxide, the resultant oxycarboxy monomer being reacted with an excess of the polyfunctional compound, many suitable alcohols, e.g. methanol, ethanol and benzyl alcohol being specified, the first stage being effected in the presence of an acidic, basic or neutral ester interchange catalyst.  In the examples, polymers are made by:- (1) to (3) reacting methanol with S -caprolactone, trimethyl caprolactone and dimethyl caprolactone, the resultant esters being reacted consecutively with ethylene oxide and ethylene glycol; (4) an ester reacted as in Examples 5(a) and (6); (7) S -caproreacted consecutively with ethylene oxide and a mixture of hexanetriol and ethylene glycol; (5) an ester derived from methanol and delta-valerolactone is reacted with ethylene oxide and the product reacted with (a) ethylene glycol and (b) an ethylene oxide adduct of methyl 6-hydroxycaproate and ethylene glycol; (6) an adduct obtained by reacting ethylene oxide with an ester made from g -butyrolactone and methanol is prepared from methanol and S -caprolactone is lactone, ethylene glycol and ethylene oxide; (8) methyl S -caprolactone, ethylene glycol and ethylene oxide; (9) S -caprolactone, trimethylol propane and ethylene oxide; (10) a mixture so gamma-, beta- and delta-methyl-S -caprolactones, ethylene glycol and ethylene oxide; (11) a mixture of methyl-S -caprolactones, trimethylol propane and ethylene oxide; (12) S -caprolactone, ethylene glycol, ethylene oxide and propylene oxide; (13) dimethyl-S -caprolactone, ethylene glycol and ethylene oxide; (14) g -butyrolactone, trimethylol propane and ethylene oxide; (15) delta-valerolactone, ethylene glycol and ethylene oxide; (16) and (17) S -caprolactone, trimethylol propane and ethylene oxide; (18) S -caprolactone, adipic acid and ethylene oxide; (19) and (20) mixed methyl-S -caprolactons and methanol, the resultant ester being reacted consecutively with ethylene oxide and ethylene glycol; (21) S -caprolactone, water and ethylene oxide and (22) S -caprolactone, ethylene glycol and ethylene oxide.  Specifications 859,639, 859,642 and 859,644 are referred to.ALSO:Foamed polyurethanes are made by reacting polyisocyanates with the oxyalkylene-carboxyalkylene polymers of the invention (see Group IV(a)).  Specifications 859,639, 859,642 and 859,644 are referred to.